Dehydrogenation processes using catalysts comprising catalytic metal on a nonacidic support

Abstract

Organic compounds are dehydrogenated by contact with a catalyst prepared by oxidizing and then sulfiding a composition comprising Group VIIIA (first or second row) catalytic metal on a nonacidic porous support, for example alumina, to produce compositions which have good dispersion of a catalytically active metal component and of sulfide species over the surface of the compositions and high activity as catalysts for the dehydrogenation of organic compounds. In one embodiment of the invention the catalyst used in the process of the invention has ratios of nickel, and/or sulfide species to peak areas of aluminum in the support, as determined by X-ray photoelectron spectroscopy (XPS), which improve their activity and stability for use as dehydrogenation catalysts. The catalyst may also have ratios of cesium, added to reduce acidity, to aluminum peak areas, as determined by XPS, which have advantages for use as dehydrogenation catalysts in respect of activity, resistance to deactivation and avoidance of side reactions.

The invention claimed is: 
     
       1. Process for dehydrogenating organic compounds which comprises: contacting a dehydrogenatable organic compound under dehydrogenation conditions with a catalyst prepared by oxidizing a composition comprising a catalytic metal selected from the group consisting of Group VIA, Group VIIIA first row and Group VIIIA second row metals and a nonacidic microporous support to obtain an oxidized composition, and sulfiding said oxidized composition. 
     
     
       2. Process according to claim 1 wherein said catalytic metal is a first-row Group VIIIA metal. 
     
     
       3. Process according to claim 2 wherein said catalytic metal is nickel. 
     
     
       4. Process according to claim 2 wherein said catalytic metal is a second-row Group VIIIA metal. 
     
     
       5. Process according to claim 4 wherein said catalytic metal is palladium. 
     
     
       6. Process according to claim 4 wherein said catalytic metal is rhodium. 
     
     
       7. Process according to claim 1 wherein said support is alumina. 
     
     
       8. Process according to claim 1 wherein said support is a zeolite. 
     
     
       9. Process according to claim 8 wherein said support is barium L zeolite. 
     
     
       10. Process according to claim 1 wherein said composition comprises a base. 
     
     
       11. Process according to claim 10 wherein said composition comprises alkali metal. 
     
     
       12. Process according to claim 11 wherein said alkali metal is cesium. 
     
     
       13. Process according to claim 1 wherein said sulfiding is in an atmosphere of hydrogen. 
     
     
       14. Process according to claim 1 wherein said oxidizing is at a temperature from about 250° to about 375° C. 
     
     
       15. Process for dehydrogenating organic compounds which comprises: contacting a dehydrogenatable organic compound under dehydrogenation conditions with a catalyst comprising sulfided nickel and nonacidic alumina, and having a ratio of the nickel 2P 3/2  peak area to the Al(2s) peak area, as determined by X-ray photoelectron spectroscopy of at least about 0.7, said ratio being determined by a spectrometer having an instrument transmission function inversely proportional to the kinetic energy of photoelectrons. 
     
     
       16. Process according to claim 15 wherein said ratio is at least about 0.8. 
     
     
       17. Process according to claim 16 wherein said ratio is at least about 1. 
     
     
       18. Process according to claim 15 wherein said catalyst comprises a base. 
     
     
       19. Process for dehydrogenating organic compounds which comprises: contacting a dehydrogenatable organic compound under dehydrogenation conditions with a catalyst comprising sulfided nickel and nonacidic alumina, and having a ratio of the sulfide S 2-  (2p) peak area to the Al(2s) peak area, as determined by X-ray photoelectron spectroscopy of at least about 0.05, said ratio being determined by a spectrometer having an instrument transmission function inversely proportional to the kinetic energy of photoelectrons. 
     
     
       20. Process according to claim 19 wherein said composition comprises a base. 
     
     
       21. Process for dehydrogenating organic compounds which comprises: contacting a dehydrogenatable organic compound under dehydrogenation conditions with a catalyst comprising sulfided catalytic metal, a cesium compound and alumina, and having a ratio of the cesium 4P 3/2  peak area to the Al(2s) peak area, as determined by X-ray photoelectron spectroscopy of at least about 0.06, said ratio being determined by a spectrometer having an instrument transmission function inversely proportional to the kinetic energy of photoelectrons. 
     
     
       22. Process according to claim 21 wherein said ratio is at least about 0.08. 
     
     
       23. Process according to claim 22 wherein said ratio is at least about 0.1. 
     
     
       24. Process for dehydrogenating organic compounds which comprises: contacting a dehydrogenatable organic compound under dehydrogenation conditions with a catalyst comprising sulfided nickel and nonacidic alumina and having: (1) a ratio of the nickel 2P 3/2  peak area to the Al(2s) peak area, as determined by X-ray photoelectron spectroscopy, of at least about 0.7, and/or   (2) a ratio of the sulfide S 2-  (2p) peak area to the Al(2s) peak area, as determined by X-ray photoelectron spectroscopy, of at least about 0.05; said ratio being determined by a spectrometer having an instrument transmission function inversely proportional to the kinetic energy of photoelectrons.     
     
     
       25. Process according to claim 24 wherein said catalyst comprises cesium and has a ratio of the cesium 4P 3/2  peak area to the Al(2s) peak area, as determined by X-ray photoelectron spectroscopy, of at least about 0.07, said ratio being determined by a spectrometer having an instrument transmission function inversely proportional to the kinetic energy of photoelectrons XPS, of at least about 0.07.